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Recent developments in flame retardants for sustainable fire safety solutions:
Emerald Innovation™ 3000 polymeric flame retardant
Presentation to AMI Masterbatch 2013 Patrick Jacobs, Technical Business Service EMEA Great Lakes Solutions, a Chemtura business
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Agenda
Chemtura / Great Lakes Solutions Overview
Greener Innovation Strategies
Emerald InnovationTM 3000 Polymeric Flame Retardant
Introduction: structure
Fire performance vs. HBCD / other aliphatic FRs
Thermal stability in MB and at use levels
Conclusions
Global specialty chemical company listed on the New York Stock Exchange (“CHMT”)
Major markets served are energy, electronics, transportation, and agriculture
Committed to global sustainability and engineering chemical solutions that meet our customers’ evolving needs
More than 4,300 employees worldwide
Manufactures in 31 countries and sells products in more than 100 countries
Global headquarters in Philadelphia, Pennsylvania
Regional headquarters and shared service centers in Sao Paulo, Brazil; Shanghai, China; Middlebury, Connecticut; and Manchester, United Kingdom
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Great Lakes Solutions, an Industry Leader
Electrical &
Electronics
Insulation &
Furniture
Automotive
Fumigation Energy: Oilfield &
Mercury Control
Fine Chemical/
Pharmaceutical
Biocides Automotive Tires
Fumigation
Biocides
Other
Insulation &
Furniture
Electrical & Electronics
Auto
Fine Chem/ Pharma
Energy
Flame
Retardants
Brominated
Performance
Products
KE
Y B
US
INE
SS
ES
INDUSTRIES SERVED
Mercury control
Greener innovation
Rapid growth in electronics
Flame retarded energy efficient
thermal insulation
Increased global fire safety
standards
KE
Y G
RO
WT
H
DR
IVE
RS
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How Do We Move Toward Environmentally Friendly, Sustainable FR Solutions?
Great Lakes Solutions is applying a “Greener is Better” philosophy...
Greener Innovation
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Greener FR Design Strategy
Greener alternatives that – Achieve targeted fire safety standards
– Meet or exceed baseline performance and manufacturability
– Are cost effective based on total system cost
– Minimize transition costs
Strive for zero environmental release – VECAP to prevent release from manufacture to fabrication
– Durable & recyclable to allow low-risk rework and recycling
Structures that are inherently – Not persistance
– Not bioavailable
– Not toxic
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The polymeric structure of Emerald Innovation™ 3000 renders it not readily bioavailable*, thus addressing the environmental concerns that threaten the sustainability of many current products.
Emerald Innovation™ 3000 is an efficient, sustainable replacement for HBCD requiring minimal modification to current formulations or production processes.
Applicable fire safety standards covering polystyrene foam insulation can be achieved with Emerald Innovation™ 3000.
Synergists commonly used for EPS and XPS production are compatible with Emerald Innovation™ 3000.
Our strategy of greener innovation provides you with proven, sustainable alternatives
The Value of Emerald Innovation™ 3000
* Per criteria described in US Federal Register notice 40 CFR 723
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Results of Screening Versus Design for The Environment Assessment Framework
vL= very Low
L= Low
vH= very High
NE= no evidence
Source: Davis, J.W. et. al., Strategic Approach Towards Developing More Environmentally
Sustainable Flame Retardants, 12th Workshop on Brominated and Other Flame Retardants,
2011
PolyFR = Emerald Innovation™ 3000
Persistent by Design, Required for Service Life &
Stability
Low to Very Low in All Health and Environmental Effects
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Emerald Innovation™ 3000
Property Emerald Innovation™ 3000
Appearance Compacted powder
Bromine, % 64
Softening point, 0C 120
5% wt loss, 0C (Thermogravimetric Analysis (@ 10 0C/min under N2)
2620C
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Emerald Innovation™ 3000 Flammability Performance Compared to HBCD
Emerald Innovation™ 3000 demonstrates comparable fire retardant efficiency versus HBCD at similar bromine levels
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Comparison to Partially Aliphatic Bromine Source
Formulation % Br % Synergist DIN 4102 B2 Swiss Fire Testing
(5.1)
HBCD 1.60 - Pass Pass
Emerald Innovation™ 3000 1.00 0,2 Pass Pass
FR1 1.90 0,25 Fail Fail
FR1 2,40 0.30 Fail Fail
Data provided by the Dow Chemical Company
FR1 = Tetrabromobisphenol A bis (2,3-dibromopropyl ether), a.k.a. PE-68™
Synergist = An organic compound having labile C-C linkages capable of generating radicals in the early
stages of ignition process which can reduce the molecular weight of the host polymer.
Aliphatic C-Br bonds are the key to efficiency in PS foams
Only one half of the bromine in FR1 is aliphatic
FR1 is not effective at >50% higher load level
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Thermal Stability Testing
Emerald Innovation™ 3000 is an efficient FR for extruded polystyrene (XPS) but lacks thermal stability, like HBCD, during processing
Goal is to determine a suitable stabilization package for processing Emerald Innovation™ 3000.
All formulations were run on a single screw extruder for multi-pass evaluation in Polystyrene Nova PS1600 @ 200˚C
Pellets from extrusion pass 1, 3 & 5 were set aside for melt flow and color determination on molded plaques
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Color and MFI Data 24-01 24-02 24-03 24-04 24-05 24-06 24-07 24-08 24-09 24-10
% Emerald InnovationTM 3000 - 2 2 2 2 2 2 2 2 2
% Epon 164 - - 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
% Anox 20 - - 0.1 0.1 0.15 - - - 0.1 -
% Naugard 445 - - - 0.1 0.15 - 0.1 0.15 - -
% TBM6 - - - - - 0.1 0.1 0.15 - -
% Ultranox 626 - - - - - - - - 0.1 -
% Irganox 565 - - - - - - - - - 0.2
% Nova PS 1600 100 98 97.7 97.6 97.5 97.7 97.6 97.5 97.6 97.6 Color Values YI D1925
1st Pass 2.04 10.12 5.72 3.23 2.50 3.80 4.75 4.53 0.04 4.65 3rd Pass 3.51 22.90 7.62 6.01 5.24 8.60 7.82 8.25 1.11 8.03 5th Pass 3.95 44.27 7.80 9.15 7.37 13.77 12.17 12.67 2.31 11.52
WI CIE 1st Pass 70.52 39.07 50.45 57.16 58.26 56.58 53.69 53.97 66.02 52.39 3rd Pass 64.23 -2.55 42.88 47.49 48.8 40.32 43.13 42.18 61.34 40.79 5th Pass 63.06 -75.81 41.78 36.8 41.46 24.64 29.92 28.83 56.71 29.42
MFI @ 200C/5kg, g/10min 1st Pass 7.04 7.62 6.09 5.55 5.86 5.86 5.08 6.08 5.39 5.71 3rd Pass 7.85 8.79 6.11 6.23 6.15 6.38 6.53 6.58 5.64 6.16 5th Pass 8.67 9.67 6.64 6.58 6.87 7.04 7.40 7.47 5.69 6.38
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Yellowness Index
0
5
10
15
20
25
30
35
40
45
50
1st pass
3rd pass
5th pass
0.1% Anox 20/0.1% Ultranox 626/ 0.2% Epon 164 appears to be most effective
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Processing at Higher Temperature
Extruder Temperature Profile, °C 200, 230, 260, 260 250, 260, 260, 260
% Emerald Innovation™ 3000 2 2
% Epon 164 0.4 0.4
% Anox 20 0.1 0.1
% Ultranox 626 0.2 0.2
% Nova PS 1600 97.3 97.3
YI D1925 6.57 18.97
WI CIE 44.12 6.67
MFI @ 200°C / 5kg / g/10min 5.96 6.16
Increasing the Stabilization package and using a gradually increasing temperature profile in extrusion allows for processing at higher temperatures
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Emerald Innovation™ 3000 thermal stability testing vs. stabilised HBCD
Masterbatch samples
62.5% FR + Epon 164/Anox 20/Ultranox 626 (6.25%/3.125%/3.125%)
Extrusion temps: 190, 195, 200, 200˚C
Masterbatch pellets pressed via compression molding into thin plaques
Compression molding carried out at 150˚C
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Emerald Innovation™ 3000 thermal stability testing vs. HBCD
Emerald Innovation™ 3000 MB Stabilised HBCD MB
Masterbatch compression molded
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Masterbatch pellets subject to oven aging at 200˚C for 30 min.
Let-down in Polystyrene (zinc free) @ 2% FR loading Let-down samples injection molded into 0.8mm plaques and
subject to oven aging at 200˚C for 30 min.
Emerald Innovation™ 3000 thermal stability testing vs. HBCD
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Stabilised HBCD MB Emerald Innovation™ 3000 MB
Emerald Innovation™ 3000 thermal stability testing vs. HBCD
Masterbatch pellets subject to oven aging
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Stabilised HBCD Emerald Innovation™ 3000
Emerald Innovation™ 3000 thermal stability testing vs. HBCD
Let-down at 2% and subject to oven aging
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Summary
Emerald Innovation™ 3000 is a highly efficient fire safety solution for XPS foam insulation.
An optimized stabiliser solution (0.1% Anox 20/0.1% Ultranox 626 along with 0.2% Epon 164) has been developed for XPS containing Emerald Innovation™ 3000.
This stabilisation package produced an excellent balance of Yellowness Index, Whiteness Index and MFI of Polystyrene after 5 extrusion passes.
Emerald Innovation™ 3000 stabilised with the optimized package has a better thermal stability compared to stabilised HBCD.
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Acknowledgements and Thanks
Great Lakes Solutions Applications Research Laboratory West Lafayette, Indiana
Dr. Subra Narayan
Harry Hodgen
Julie McKeown
Ken Bol
For More Information: [email protected]
